Control of insects



Patented Feb. 3, 1 948 common or msEcrs William F. Hester, Drexel Hill,2a., asaignor to Bohm & Haas Company, Philadelphia, Pa... a

corporation of Delaware riginal application June 24, 1943,

No Drawing.

Serial No. 492,133.

I Claims. This invention concerns compounds eral formula:

wherein X represents a halogen, Ar represents an aryl nucleus, nrepresents an integer from 1 to 5, inclusive, and 111 represents aninteger from 1 to 3, inclusive. It deals also with insecticidalcompositions containing these compounds.

The compounds corresponding to the above formula may be prepared byreacting a halogenated aryl sulfonyl halide with a nitroaryl amine. Thereaction may be carried out, if desired, in an organic solvent, such asbenzene or pyridine. Aqueous alkali, such as solutions of sodium orpotassium hydroxide, may be present during the reaction or may be addedsubsequent to the initial condensation. There may also be used toadvantage, particularly in organic solvents, a quaternary ammoniumhydroxide, such as benzyl trimethyl ammonium hydroxide. In a preferredmethod, the condensation is carried out in the presence of an organicamine, such as pyridine, which serves both as solvent and as a basicreagent.

There are other methods for forming the desired compounds, including thecondensation of a halogenated aryl sulfonyl halide with an arylaminefollowed by nitration. The nitration involves primarily the aryl ringcarrying the amino group. When this is a benzene ring, the first nitrogroup enters mostly para to the amino group with only a small proportiongoing to the ortho position.

As a halogenated aryl sulfonyl halide, there may be used mono, di, tri,tetra, or penta halosubstituted aryl sulfonyl chlorides or bromides.Typical of these are p-ClCeH4SOzC1,

The sulfonyl halides may have neutral nuclear substituents other thanchlorine or bromine, as has been indicated. These substituents includesuch groups as alkyl and. other aliphatic hydroof the gencarbon groups,such as ethyl, propyl, butyl, text.-

Divided and this application ltiay 3, 1944, Serial No. 533.953

butyl, octyl, isooctyl, wwy-tetramethyl butyl. undecenyl, allyl, etc.,aryl, 'such as phenyl, aralkyl, such as benzyl, methylbenzyl,butylbenzyl, etc., cycloaliphatic, such as cyclohexyl, methylcyclohexyl, etc., alkoxy, such as methoxy or ethoxy, aryloxy, such asphenoxy, ac'yl, such as CHaCO, CaHsC-, etc., nitro, other halo, or otherneutral groups.

The nitroarylamines include any of the nitroanilines such as p-,' m-, oro-mononitroaniline, the variousdinitroanilines and trinitroanilines, andnitroanilines having other neutral substituent groups, such as methyl,ethyl, propyl, butyl, amyl, etc., phenyl, benzyl, acetyl, chloro, orbromo-. There may likewise be used polynuclear nitroarylamines, such asthe nitronaphthylamines. Furthermore, as has been indicated above, anaminoaryl group which is not nitrated may be reacted 'with a haloarylsulfonyl halide and mtration'subsequently effected. In such case,aniline, naphthylamine, or other polynuclear arylamine may be used.

The following examples illustrate typical methods for the preparation ofhalogenated aryl suli'onamidonitroaryl compounds.

Example 1 4-BTCsH4SO2NHC6H4NO2-4.-T0 a solution of 27.6 parts of4-NO2C0H4NH2 in 63 parts of pyridine was slowly added 51 parts of4-BlCsH4SO2Cl. The reaction was controlled by external cooling. When thereactants had been mixed, the reaction mixture was stirred for fourhours. It was then diluted with ice water, to which had been added about100 parts of concentrated hydrochloric acid. A tarry product'wasprecipitated and separated. It was recrystallized from acetic acid andthen from alcohol to give a crystalline product melting at 177-179 C.and corresponding in composition to 4BrCoH4SO2NHCeH4NO2-4.

Example 2 3,4-Cl2CtHsSO2NHCsH4NO2-4.--T0 a solution of 27.6 parts of4-NOzCeH4NHn in 63 parts of pyridine there was slowly added 49 parts of3,4-Cl2CaH3SO2Cl.

The reaction mixture was cooled externally during the addition and thenstirred for four hours. The mixture was then diluted with ice watercontaining about parts Cl and 9.41% of 8, corresponding to theoreticalvalues of,20.45% of Cl and 9.22% of S for 3,4-Cl2CeHaSOiNHCeH4NO2-4 Bysimilar methods, there may be prepared related compounds, such as:

GNOM- NO: O O- NO Q O I NO: I

BIQEOINH r .N a

water at the rate of seven ounces person.

4 many kinds of insects. Atthe same time, they are not phytocidal orirritating to the skin of personnel handling and applying them. Thesecompounds possess stability to light, air, and water, which permitstheir effective application over a considerable period of time. Thephysical properties of this classof compounds are such that they may bereadily applied with or without diluents. They are well retained onfoliage. Furthermore, some of the compounds of this class have suitableproperties as to solubility, density,

etc., which permit their use on the surface of water for the control ofmosquito larvae.

The solids of this invention can be finely ground and sprayed or dustedonto water surfaces. The powder remains in the surface, and. since it isstable to light, air, and water, it remains eifective for long periodsof time. The compound 3,4-Cl2CcHsSOaNHCeH4NO2-4 was dusted on It gave akill of mosquito larvae of 72%. This result may. be compared with thatobtained with Paris green, one of the few known insecticides effectivefor the same purpose. It required fourteen ounces per acre of Parisgreen to give the same control. At fourteen to sixteen ounces per acrein repeated experiments, Paris green gave 60% to 80% control. At aconcentration of fourteen ounces per acre, the new compound gave a 100%kill of larvae.

This same compound was mixed with magnesiumcarbonate and applied tobeans infested with Southern army worm. When used at as The abovecompounds may be summarized by the formulae:

XsphenylSOzNHphenyl (N02) m While these compounds are generally theeasiest to prepare and include new compounds of exceptional insecticidalactivity, there are compounds formed with naphthyl, phenanthryl, or

'anthryl groups which, also have considerable 78.1118, SllGh 88:

omnONo,

It has been found that the compounds of the type:

XsArSQaNZHAHNOaM low a concentration as one-half pound per 100 gallonsof water. it gave a 100% kill of this worm. There are but few compoundswhich show any control of the army worm.

A spray'containing one pound of -Bl'CeHrSOaNHCeHeNOrper 100 gallons ofspray likewise give 100% kill of army worm and, in general, othercompounds of the same type seem exceptionally effective against thispest.

These compounds have also been found exceptionally eifective againstaphids on various kinds of plants and thus effective at considerabledilution. For applications of this type, there may be used a compositionsuch as:

I Parts- Toxicant 1 Spreader 1 Talc 9a The toxicant may be coated on thetalc or other finely divided inert carrier from a solution in an organicsolvent which is evaporated from the impregnated solid. As a spreader,there may be used a soap or a synthetic detergent, such asoctylphenoxyethyl sodium sulfate or cetyl dimethyl benzyi ammoniumchloride.

The above preparations are suitable fOr use pripossess markedinsecticidal properties against as dusts. although they may be used insprays Another formula particularly useful in sprws is as follows:

Parts Toxicant 1 Magnesium carbonate 3 Spreader Water 951.5

was thus applied at 1 to 4,000, the aphids were wiped out. This compoundlikewise gave complete control of red spider. In no case did any damageresult to the plants sprayed. Control experiments made parallel to theabove tests showed that sprays containing an accepted, standardcommercial preparation at 1 to 4,000 killed only 50% of the aphids and20% of the red spiders.

The compounds ,of this invention have also been applied to woolenfabrics which were then placed in a. cabinet with carpet beetles. Thebeetles were killed in a short time. Fresh colonies of beetles were usedwith the same result. Tests over a three-year period showed that thefabrics retained their efiectiveness over this entire period.

For this-application, approximately 2% solutions were made in volatileorganic solvents, wool treated therewith, the solvent evaporated fromthe wool, and the wool aged six weeks before being placed in the cabinetwith the carpet beetles. The tests with such beetles are generallypreferred over the common clothes moth and are more severe. The tests,therefore, indicate that the woolen fabrics treated with halogenatedaryl sulfonamidonitroaryl compounds are well mothproofed.

water in finely divided form a compound of the formula:

x. (Non,

3 wherein x is a halogen, n is an integer from one to'flve, inclusive,and m is an integer from one to three, inclusive.

2. A method of controlling mosquito larvae in water which comprisesapplying to the surface of water in finely divided form a compound ofthe formula: I

3,4-ChCoHaSOaNHCeH4NOa 3. A method of controlling mosquito larvae inwater which comprises applying to the surface of water in finely dividedform a compound of the formula: I

4i-BrCeH4SO2NHCoH4NO2 Xv. In

wherein X is a halogen, n is an integer from one tofive, inclusive, andm is an integer from one to The particular form or composition in whichthe new compounds are used as insecticides is dictated by the type ofapplication desired, that is, whether spray or dust, the particulainsects being combatted, and the nature of the other materials, if any,in the composition. Thus, as has been shown, the compounds may be mixedwith or sprayed on finely divided materials, such as clay, talc, chalk,magnesium carbonate, walnut shell flour, wood flour, etc. Also,,thecompounds of this invention may be taken up in an organic solvent andapplied as an emulsion or aerosol therefrom.

The compounds of this invention may be used as the sole toxic agent oras one of several such agents to give a plurality of effects or a singleimproved effect. Additional agents which may be used in conjunction withthe compounds of this invention are 'rotenone, pyrethrins, nicotine,arsenates, oils from tars, or petroleum or of vegetable or animalorigin, organic thiocyanates, etc. The compounds may also be used inconjunction with fungicides such as basic copper sulfate, cuprous oxide,copper oxychloride, dithiocarbamates, thiuram sulfides, etc.

The present application constitutes a division of my application SerialNo. 492,133, flied June 24, 1943, now Patent Number 2,402,623 issuedJune 25, 1946.

I claim:

1. A method of controlling mosquito larvae in water which comprisesapplyingto the surface of three, inclusive.

5. The process of controlling insects which comprises supplying theenvironment of said insects with a compound of the formula:

c1. (Non.

wherein m is an integer from one to three, inclusive.

' 6. The process of controlling insects which comprises supplying theenvironment of said insects with a compound of the formula:

wherein m is an integer from one to three, inelusive.

'7. The process of controlling insects which comprises supp theenvironment of said insects with a compound of the formula:

X. NO:

wherein X is a halogen and n is an integer from one to five, inclusive.

8. The process of controlling insects on livin plants which comprisesapplying to said plants a composition which contains as an active agenta compound of the formula:

compound of the formula:

10. The process of controlling insects on livin plants which comprisesapplying to said plants a 7 8 composition which contains as an activeagent 2. UNITED STATES PA'LENTB compound 01 the formula: Numb, Name 1Date I 1,955,207 stutter et a1. Apr. 17, 1934 O O 62,276 Huismann et a1.June 12, 1934 6 2,292,998 Hentrlch et a1. Aug. 11, 1942 WILLIAM F.HESTER. 2,402,623 Hester June 25, 1946 REFERENCES crmn M t an OTHER 3 It 9.]. Jr. 0 Economic Entomology The following references are of recordin the e c e me of, this patent; 10 ml. 34, 1941, pages 308-309.

